EP0533670B1 - Adding a malodorant to oxygen gas and suitable liquid odorising mixture - Google Patents

Adding a malodorant to oxygen gas and suitable liquid odorising mixture Download PDF

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Publication number
EP0533670B1
EP0533670B1 EP90910956A EP90910956A EP0533670B1 EP 0533670 B1 EP0533670 B1 EP 0533670B1 EP 90910956 A EP90910956 A EP 90910956A EP 90910956 A EP90910956 A EP 90910956A EP 0533670 B1 EP0533670 B1 EP 0533670B1
Authority
EP
European Patent Office
Prior art keywords
gas
malodorant
mercaptan
mixture
sulphide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP90910956A
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German (de)
French (fr)
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EP0533670A1 (en
Inventor
Erik Smars
Timo Suominen
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AGA AB
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AGA AB
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Application filed by AGA AB filed Critical AGA AB
Priority to AT90910956T priority Critical patent/ATE122264T1/en
Publication of EP0533670A1 publication Critical patent/EP0533670A1/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/003—Additives for gaseous fuels
    • C10L3/006—Additives for gaseous fuels detectable by the senses
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B01F23/10—Mixing gases with gases
    • B01F23/12—Mixing gases with gases with vaporisation of a liquid

Definitions

  • the present invention relates to a method of adding a malodorant to a oxygen gas which is distributed to a consumer station, so that persons present in the surroundings of the distribution system will be warned that the surrounding atmosphere contains more than the highest permitted concentration of gas, therewith constituting the risk of fire explosion.
  • Oxygen can cause extremely comprehensive fire and explosion damage if it leaks into the surroundings ambient of the distribution system and/or the consumer station and therewith enriches the ambient air or atmosphere.
  • DE-B-1,185,330 discloses a method for the odorisation of gases (only hydrocarbon gases are explicitly mentioned) with a liquid master mixture.
  • the liquid master mixture consists of a malodorant dissolved in a liquid hydrocarbon, primarily propane and butane and mixtures thereof. Carbon dioxide is not mentioned as a liquid for dissolving the malodorant.
  • the master mixture is injected into the gas to be odorized. After the injection the liquid master mixture evaporates in the hydrocarbon gas to be odorized.
  • Gwf 111 (1970), Heft 3, p 159-166 discloses several methods to introduce a malodorant into a stream of a gaseous hydrocarbon. A great number of malodorants are disclosed.
  • On method is to use a wick to draw a liquid malodorant into a gas stream. Another method is to bring part of the gas to be odorized to pass over a large surface of the malodorant and to combine this odorized part with the reminder of the hydrocarbon gas. A third method is to inject the pure or diluted liquid malodorant into a stream of hydrocarbon gas (see fig.4).
  • FI-B-78172 describes an improved method of adding a malodorant to oxygen gas so that if the air becomes enriched with oxygen, individuals in the near vicinity are warned that there is an imminent risk of explosion.
  • This improved method eliminates the need of handling toxic malodorants by the consumer, thereby avoiding the risk of explosion created by the addition of such malodorants.
  • a gaseous mixture of malodorant and a carrier gas in this case oxygen, a so-called master gas
  • the master gas is admixed with oxygen gas distributed to the consumer in an amount such that the malodorant has a concentration of 5-50 ppm in the consumer gas.
  • the master gas contains solely oxygen and malodorant, for example dimethyl sulphide, DMS
  • DMS dimethyl sulphide
  • this application teaches a method of producing a master gas consisting of oxygen and a malodorant, in this case dimethyl sulphide.
  • the master gas container is first filled with a mixture of dimethyl sulphide and nitrogen or helium gas.
  • the dimethyl sulphide is present in a concentration of 0.5-2.5 mole per cent.
  • Oxygen gas is then introduced until a desired working pressure, e.g. 200 bars, is obtained in the container.
  • the object of the present invention is to provide a method for producing master gas for admixture with oxygen, and which avoids the aforesaid drawbacks.
  • the method is characterized by dissolving a malodorant in the form of an organic sulphur compound or a mixture of two or more organic sulphur compounds, said compounds being selected from tetrahydrothiophene, methyl mercaptan, ethyl mercaptan, propyl mercaptan, butyl mercaptan, dimethyl sulphide, diethyl sulphide and methylethyl sulphide, in condensed carbon dioxide in a pressure vessel, thereby obtaining in the pressure vessel a liquid phase, consisting of a solution of the malodorant in the condensed gas, the malodorant having a concentration of 0.5-10 mole per cent, and a gas phase; and by removing only the liquid phase from the vessel, completely vaporizing said liquid phase and adding the resulting vapor phase to the oxygen gas distributed to the consumer. It is preferred to add the master gas to the oxygen gas in a quantity such that the malodorant concentration in said oxygen gas is 1-20 pp
  • the invention also relates to a liquid master mixture consisting of liquid carbon dioxide, containing a dissolved malodorant of the aforesaid kind.
  • the malodorant which is an ill-smelling organic compound or a mixture of two or more such compounds, is introduced into the carrier gas, i.e. condensed carbon dioxide, in an amount of 0.5-10 mole per cent, calculated on the total quantity of gas.
  • the aforesaid ill-smelling substances methyl mercaptan, ethyl mercaptan, propyl mercaptan, butyl mercaptan, tetrahydrothiophene, dimethyl sulphide, diethyl sulphide and methyl ethyl sulphide, are soluble in the condensed gas in quantities sufficient to enable the method to be applied in practice.
  • the pressure in the resultant gas phase will vary when the gas mixture is stored at differing temperatures.
  • the malodorant content of the condensed gas is only affected to a negligible extent at temperatures within the range of -40°C to +50°C.
  • Admixture of the master gas, i.e. the carrier gas diluted with the malodorant, with the oxygen gas is effected by first removing the liquid master mixture of carrier gas and malodorant from the pressure vessel in which the mixture is stored, and completely vaporizing the liquid phase and then introducing the resulting gaseous mixture into the oxygen gas in quantities such that the concentration of malodorant in the oxygen gas will preferably lie within the range of 1-50 ppm (1.0001-0.0050 mole per cent), more preferably within the range of 1-20 ppm.
  • the master gas i.e. the gas mixture consisting of malodorant and carbon dioxide
  • a gas mixer of more or less conventional kind is connected to the system upstream of the inlet to the pipe network.
  • the oxygen gas and the master gas are mixed in desired proportions in this mixer.
  • the gas mixer includes a control system by means of which the ratio between the flow of master gas and the flow of consumer gas can be constantly maintained at a constant level. For example, if the master gas contains 2 mole per cent malodorant and the oxygen gas shall contain 4 ppm malodorant, the aforesaid ratio shall be 1:5000.
  • the vaporized mixture When the oxygen gas is distributed to the consumer in a high pressure container, the vaporized mixture, the master gas, is first introduced into the container in a quantity such that the desired proportion of malodorant is obtained when subsequently introducing the oxygen gas into the container to the desired container pressure.
  • the oxygen gas containing the malodorant added thereto in accordance with the invention will therefore contain a given amount of carrier gas, i.e. carbon dioxide, in addition to the malodorant.
  • carrier gas i.e. carbon dioxide
  • the carrier-gas content of the master gas is, for instance, 95 mole per cent, i.e. the master gas contains 5 mole per cent malodorant, an admixture has been effected with one part of master gas to 5000 parts of oxygen gas, the malodorant content will be 10 ppm and the carrier gas content, i.e. carbon dioxide, will be 0.02 mole per cent.
  • This carrier gas content will not have any noticeable negative effect when using oxygen which contains a malodorant for different industrial flame processes, such as welding, cutting and heating work.
  • the purity of oxygen produced industrially today is often some tens of per cent units above the degree of purity required for gas cutting work, for example.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Treating Waste Gases (AREA)
  • Disinfection, Sterilisation Or Deodorisation Of Air (AREA)
  • Detergent Compositions (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Gas Separation By Absorption (AREA)

Abstract

The invention has regard to a method of adding a malodorant to a consumer gas, such as oxygen, natural gas, propane gas, town gas or some other combustible gas, an odorless, toxic gas or a more or less inert gas distributed to a consumer station for the purpose of warning individuals in the surroundings that there is a risk of fire, explosion, suffocation, toxicity or some other risk due to the presence of consumer gas in the surrounding atmosphere as a result of leakage, negligence or some other reason, said method including the step of mixing a master gas, i.e. a carrier gas diluted with malodorant, with the consumer gas. The characteristic feature of the method comprises dissolving the malodorant in the form of an organic sulphur compound or a mixture of two or more organic sulphur compounds, these compounds comprising tetrahydrothiophene, methyl mercaptan, ethyl mercaptan, propyl mercaptan and butyl mercaptan, dimethyl sulphide, diethyl sulphide and methylethyl sulphide, in condensed carbon dioxide, sulphur hexafluoride or dinitrogen oxide in a pressure vessel, thereby obtaining in the pressure vessel a liquid phase, consisting of a solution of malodorant in the condensed gas, and a gas phase; and removing the liquid phase from the vessel, vaporizing said liquid phase and supplying the resultant vapor phase to the consumer gas, which is distributed to the consumer. The invention also relates to a gas mixture consisting of the malodorant in condensed carbon dioxide, sulphur hexafluoride or nitrous oxide.

Description

  • The present invention relates to a method of adding a malodorant to a oxygen gas which is distributed to a consumer station, so that persons present in the surroundings of the distribution system will be warned that the surrounding atmosphere contains more than the highest permitted concentration of gas, therewith constituting the risk of fire explosion. Oxygen can cause extremely comprehensive fire and explosion damage if it leaks into the surroundings ambient of the distribution system and/or the consumer station and therewith enriches the ambient air or atmosphere.
  • DE-B-1,185,330 discloses a method for the odorisation of gases (only hydrocarbon gases are explicitly mentioned) with a liquid master mixture. The liquid master mixture consists of a malodorant dissolved in a liquid hydrocarbon, primarily propane and butane and mixtures thereof. Carbon dioxide is not mentioned as a liquid for dissolving the malodorant.
  • The master mixture is injected into the gas to be odorized. After the injection the liquid master mixture evaporates in the hydrocarbon gas to be odorized.
  • Gwf 111 (1970), Heft 3, p 159-166 discloses several methods to introduce a malodorant into a stream of a gaseous hydrocarbon. A great number of malodorants are disclosed.
  • On method is to use a wick to draw a liquid malodorant into a gas stream. Another method is to bring part of the gas to be odorized to pass over a large surface of the malodorant and to combine this odorized part with the reminder of the hydrocarbon gas. A third method is to inject the pure or diluted liquid malodorant into a stream of hydrocarbon gas (see fig.4).
  • WO90/06170 claiming priority from November 30, 1988 and published on June 14, 1990 discloses the subject matter of the claimed invention. However, this document was published after the filing date of the present application and does not belong to the state of the art according to Article 54 (3) EPC, since the conditions of Article 158 (2), 2nd sentence, are not met.
  • FI-B-78172 describes an improved method of adding a malodorant to oxygen gas so that if the air becomes enriched with oxygen, individuals in the near vicinity are warned that there is an imminent risk of explosion. This improved method eliminates the need of handling toxic malodorants by the consumer, thereby avoiding the risk of explosion created by the addition of such malodorants. In a space or chamber provided for this purpose, there is produced a gaseous mixture of malodorant and a carrier gas, in this case oxygen, a so-called master gas, by adding to the oxygen gas a malodorant in a concentration of 1,000-10,000 ppm. In a separate space or chamber, isolated from the aforesaid space, the master gas is admixed with oxygen gas distributed to the consumer in an amount such that the malodorant has a concentration of 5-50 ppm in the consumer gas.
  • However, when the master gas contains solely oxygen and malodorant, for example dimethyl sulphide, DMS, problems can occur when filling the master gas container. For instance, it is unavoidable to lie in a concentration range during part of the filling procedure in which the mixture is combustible, at least in a part of the container. There is thus a risk of ignition and explosion.
  • One method of avoiding this risk is described in FI-B-78173. Thus, this application teaches a method of producing a master gas consisting of oxygen and a malodorant, in this case dimethyl sulphide. According to this described method, the master gas container is first filled with a mixture of dimethyl sulphide and nitrogen or helium gas. The dimethyl sulphide is present in a concentration of 0.5-2.5 mole per cent. Oxygen gas is then introduced until a desired working pressure, e.g. 200 bars, is obtained in the container.
  • One drawback with the master gas produced in with this described method, however, is that during transportation and storage, the master gas must not be subjected to temperatures which are so low as to condense the malodorant. For example, in the case of a master gas which consists of 0.2 mole per cent dimethyl sulphide, 9.8 mole per cent helium or nitrogen and 90 mole per cent oxygen at 200 bars, dimethyl sulphide will condense when the temperature falls beneath 13°C. When the master gas container is subsequently heated to a temperature above 13°C, a very long time elapses before the condensed dimethyl sulphide has again returned to a gaseous state.
  • The object of the present invention is to provide a method for producing master gas for admixture with oxygen, and which avoids the aforesaid drawbacks.
  • The method is characterized by dissolving a malodorant in the form of an organic sulphur compound or a mixture of two or more organic sulphur compounds, said compounds being selected from tetrahydrothiophene, methyl mercaptan, ethyl mercaptan, propyl mercaptan, butyl mercaptan, dimethyl sulphide, diethyl sulphide and methylethyl sulphide, in condensed carbon dioxide in a pressure vessel, thereby obtaining in the pressure vessel a liquid phase, consisting of a solution of the malodorant in the condensed gas, the malodorant having a concentration of 0.5-10 mole per cent, and a gas phase; and by removing only the liquid phase from the vessel, completely vaporizing said liquid phase and adding the resulting vapor phase to the oxygen gas distributed to the consumer. It is preferred to add the master gas to the oxygen gas in a quantity such that the malodorant concentration in said oxygen gas is 1-20 ppm.
  • The invention also relates to a liquid master mixture consisting of liquid carbon dioxide, containing a dissolved malodorant of the aforesaid kind.
  • The malodorant, which is an ill-smelling organic compound or a mixture of two or more such compounds, is introduced into the carrier gas, i.e. condensed carbon dioxide, in an amount of 0.5-10 mole per cent, calculated on the total quantity of gas. The aforesaid ill-smelling substances, methyl mercaptan, ethyl mercaptan, propyl mercaptan, butyl mercaptan, tetrahydrothiophene, dimethyl sulphide, diethyl sulphide and methyl ethyl sulphide, are soluble in the condensed gas in quantities sufficient to enable the method to be applied in practice. The pressure in the resultant gas phase will vary when the gas mixture is stored at differing temperatures. The malodorant content of the condensed gas is only affected to a negligible extent at temperatures within the range of -40°C to +50°C.
  • Admixture of the master gas, i.e. the carrier gas diluted with the malodorant, with the oxygen gas is effected by first removing the liquid master mixture of carrier gas and malodorant from the pressure vessel in which the mixture is stored, and completely vaporizing the liquid phase and then introducing the resulting gaseous mixture into the oxygen gas in quantities such that the concentration of malodorant in the oxygen gas will preferably lie within the range of 1-50 ppm (1.0001-0.0050 mole per cent), more preferably within the range of 1-20 ppm.
  • When the master gas, i.e. the gas mixture consisting of malodorant and carbon dioxide, is to be admixed with oxygen gas which is distributed to various consumer stations through a pipe network or a through a central gas system, a gas mixer of more or less conventional kind is connected to the system upstream of the inlet to the pipe network. The oxygen gas and the master gas are mixed in desired proportions in this mixer. The gas mixer includes a control system by means of which the ratio between the flow of master gas and the flow of consumer gas can be constantly maintained at a constant level. For example, if the master gas contains 2 mole per cent malodorant and the oxygen gas shall contain 4 ppm malodorant, the aforesaid ratio shall be 1:5000.
  • When the oxygen gas is distributed to the consumer in a high pressure container, the vaporized mixture, the master gas, is first introduced into the container in a quantity such that the desired proportion of malodorant is obtained when subsequently introducing the oxygen gas into the container to the desired container pressure.
  • The oxygen gas containing the malodorant added thereto in accordance with the invention will therefore contain a given amount of carrier gas, i.e. carbon dioxide, in addition to the malodorant. When the carrier-gas content of the master gas is, for instance, 95 mole per cent, i.e. the master gas contains 5 mole per cent malodorant, an admixture has been effected with one part of master gas to 5000 parts of oxygen gas, the malodorant content will be 10 ppm and the carrier gas content, i.e. carbon dioxide, will be 0.02 mole per cent. This carrier gas content will not have any noticeable negative effect when using oxygen which contains a malodorant for different industrial flame processes, such as welding, cutting and heating work. The purity of oxygen produced industrially today is often some tens of per cent units above the degree of purity required for gas cutting work, for example.

Claims (3)

  1. A method of adding a malodorant to oxygen gas distributed to a consumer station for the purpose of Warning individuals in the surroundings that there is a risk of fire or explosion due to the presence of excess oxygen gas in the surrounding atmosphere as a result of leakage, negligence or some other reason, said method including the step of mixing a master gas, i.e. a carrier gas diluted with malodorant, with the oxygen gas, characterized in that said method comprises preparing a liquid master mixture by dissolving the malodorant in the form of an organic sulphur compound or a mixture of two or more organic sulphur compounds, these compounds being selected from tetrahydrothiophene, methyl mercaptan, ethyl mercaptan, propyl mercaptan, butyl mercaptan, dimethyl sulphide, diethyl sulphide and methylethyl sulphide, in condensed carbon dioxide in a pressure vessel to a concentration of 0.5-10 mole per cent, whereby from the vessel containing both gaseous and liquid phase only liquid is discharged from the vessel, said liquid is vaporized completely and thereafter said vaporized master gas mixture is added to the oxygen.
  2. The method according to Claim 1, characterized by adding the master gas to the oxygen in an amount such that the concentration of malodorant in the oxygen is 1-20 ppm.
  3. A liquid master mixture consisting of a malodorant in the form of an organic sulphur compound or a mixture of two or more organic sulphur compounds, these compounds being selected from tetrahydrothiophene, methyl mercaptan, ethyl mercaptan, propyl mercaptan, butyl mercaptan, dimethyl sulphide, diethyl sulphide and methylethyl sulphide, dissolved in condensed carbon dioxide in a concentration of 0.5-10 mole per cent.
EP90910956A 1990-05-22 1990-05-22 Adding a malodorant to oxygen gas and suitable liquid odorising mixture Expired - Lifetime EP0533670B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT90910956T ATE122264T1 (en) 1990-05-22 1990-05-22 ODORIZATION OF OXYGEN GAS WITH A SMELLING SUBSTANCE AND LIQUID MIXTURE SUITABLE THEREFOR.

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/SE1990/000340 WO1991017817A1 (en) 1990-05-22 1990-05-22 Adding a malodorant to a gas and liquid gas mixture

Publications (2)

Publication Number Publication Date
EP0533670A1 EP0533670A1 (en) 1993-03-31
EP0533670B1 true EP0533670B1 (en) 1995-05-10

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Family Applications (1)

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EP90910956A Expired - Lifetime EP0533670B1 (en) 1990-05-22 1990-05-22 Adding a malodorant to oxygen gas and suitable liquid odorising mixture

Country Status (12)

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EP (1) EP0533670B1 (en)
JP (1) JPH05507022A (en)
AU (1) AU650849B2 (en)
BR (1) BR9008026A (en)
DE (1) DE69019378T2 (en)
DK (1) DK0533670T3 (en)
ES (1) ES2072441T3 (en)
LT (1) LT3095B (en)
LV (1) LV10212B (en)
NO (1) NO177456C (en)
RU (1) RU2041920C1 (en)
WO (1) WO1991017817A1 (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0646160B1 (en) * 1992-06-16 1997-06-04 Aga Aktiebolag Apparatus for adding a malodorant to a consumer gas
SE9401827L (en) * 1994-05-27 1995-05-22 Erik Smaars Konsult Ab Method and apparatus for adding odorant to a consumable gas flowing in a gas line
DE19745851B4 (en) * 1997-10-16 2006-03-23 Air Liquide Deutschland Gmbh Odoration of acetylene
RU2596954C1 (en) * 2015-08-10 2016-09-10 Общество с ограниченной ответственностью "Инновационные химические технологии" Method of detecting pre-fire situations arising due to faults in electric circuit
EA036280B1 (en) * 2015-08-10 2020-10-21 Общество С Ограниченной Ответственностью "Термоэлектрика" Autonomous device for warning of pre-fire situations
RU2622947C2 (en) * 2015-08-10 2017-06-21 Общество с ограниченной ответственностью "Инновационные химические технологии" Polymer composite material used for forming an electrical equipment local overheats signal

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1185330B (en) * 1963-01-05 1965-01-14 Koppers Gmbh Heinrich Process for the odorization of gases
FI78173B (en) * 1987-05-22 1989-02-28 Aga Ab SAETT ATT FRAMSTAELLA SK. MASTERGAS.
FI78172B (en) * 1987-03-10 1989-02-28 Aga Ab SAETT ATT TILLSAETTA LUKTAEMNE TILL OXYGENGAS.

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL174659C (en) * 1972-03-27 1984-07-16 Pennwalt Corp METHOD FOR ODORIZING LIQUEFIED, FLAMMABLE HYDROCARBON GAS.
CA1006353A (en) * 1972-10-02 1977-03-08 David K. Mulliner Method and system for odorizing liquid natural gas with thiophene
FI870146A0 (en) 1987-01-15 1987-01-15 Tauno Kalervo Koponen CASSETTE SOM TRANSFORMERAR STRAOLVAERMEN.
FI93270C (en) * 1988-11-30 1995-03-10 Aga Ab Process for adding odorant to oxygen gas

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1185330B (en) * 1963-01-05 1965-01-14 Koppers Gmbh Heinrich Process for the odorization of gases
FI78172B (en) * 1987-03-10 1989-02-28 Aga Ab SAETT ATT TILLSAETTA LUKTAEMNE TILL OXYGENGAS.
FI78173B (en) * 1987-05-22 1989-02-28 Aga Ab SAETT ATT FRAMSTAELLA SK. MASTERGAS.

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
gwf (Gas-Erdgas), 111, H.3, Feb.1970, Verlag R.Oldenburg, München; Richtlinien für die Gasodorierung, p.159-166 *

Also Published As

Publication number Publication date
LV10212A (en) 1994-10-20
LTIP183A (en) 1994-06-15
RU2041920C1 (en) 1995-08-20
DK0533670T3 (en) 1995-10-02
AU650849B2 (en) 1994-07-07
DE69019378T2 (en) 1995-09-14
EP0533670A1 (en) 1993-03-31
JPH05507022A (en) 1993-10-14
NO177456C (en) 2000-02-21
DE69019378D1 (en) 1995-06-14
LT3095B (en) 1994-11-25
NO177456B (en) 1995-06-12
LV10212B (en) 1995-08-20
NO924460D0 (en) 1992-11-19
AU6030590A (en) 1991-12-10
WO1991017817A1 (en) 1991-11-28
ES2072441T3 (en) 1995-07-16
NO924460L (en) 1992-11-19
BR9008026A (en) 1993-04-06

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